Characterization of Volatile Organic Metabolites in Lung Cancer Pleural Effusions by SPME–GC/MS Combined with an Untargeted Metabolomic Method

Headspace solid-phase microextraction and gas chromatography/mass spectrometry (HS-SPME–GC/MS) method combined with XCMS Online was tentatively applied to characterize the dysregulated volatile organic metabolites (VOMs) in benign and malignant pleural effusions. A total of 9 dysregulated feature groups were isolated from metabolic features in 35 pleural effusion samples (20 benign effusions and 15 malignant ones from lung cancer patients). Principle component analysis, partial least squares discriminant analysis (PLS-DA) and orthogonal PLS-DA were built to separate benign from malignant pleural effusion groups and to find dysregulated metabolites in significantly different amounts between the two groups. Four dysregulated VOMs such as 2-ethyl-1-hexanol, cyclohexanone, 1,2,4,5-tetramethylbenzene and naphthalene were selected according to the variable influence on the projection value. The concentration of the four dysregulated VOMs in benign and malignant effusions were further determined by external standard method. The median concentrations of 4 VOMs in malignant effusion samples were from 4.7 to 91,121.9 nM, whereas their median levels were only 1.9–318.3 nM in benign ones. The results show that the proposed SPME–GC/MS-based metabolomic approach combined with XCMS Online data processing is a simple, rapid and available method for the characterization of dysregulated VOMs in malignant and benign pleural effusions.     

Polarization-maintaining buffered Fourier domain mode-locked swept source for optical coherence tomography

A polarization-maintaining buffered Fourier domain mode-locked (FDML) swept source with a center wavelength of 1300 nm is demonstrated. The scanning rate of the buffered FDML swept source is doubled without sacrificing the output power of the swept source by combining two orthogonally polarized outputs with a polarization beam combiner. The stability of the swept source is improved because the polarization state of the laser beam inside the laser cavity is maintained without the use of any polarization controllers. The swept source is capable of an edge-to-edge tuning range of more than 150 nm and a FWHM range of 95 nm at a 102 kHz sweeping rate and with an average power of 12 mW. A swept source optical coherence tomography (SSOCT) system is developed utilizing this buffered FDML swept source. The axial resolution of the SSOCT system is measured to be 9.4 μm in air. The sensitivity of the SSOCT system is 107.5 dB at a depth of 0.25 mm with a 6 dB roll-off at a depth of 2.25 mm.     

A Multi‐responsive Fluorescent Probe Reveals Mitochondrial Nucleoprotein Dynamics with Reactive Oxygen Species Regulation through Super‐resolution Imaging

Understanding the biomolecular interactions in a specific organelle has been a long‐standing challenge because it requires super‐resolution imaging to resolve the spatial locations and dynamic interactions of multiple biomacromolecules. Two key difficulties are the scarcity of suitable probes for super‐resolution nanoscopy and the complications that arise from the use of multiple probes. Herein, we report a quinolinium derivative probe that is selectively enriched in mitochondria and switches on in three different fluorescence modes in response to hydrogen peroxide (H₂O₂), proteins, and nucleic acids, enabling the visualization of mitochondrial nucleoprotein dynamics. STED nanoscopy reveals that the proteins localize at mitochondrial cristae and largely fuse with nucleic acids to form nucleoproteins, whereas increasing H₂O₂ level leads to disassociation of nucleic acid–protein complexes.     

An Energy Investigation into 1D/2D Oriented‐Attachment Assemblies of 1D Ag Nanocrystals

In the field of oriented‐attachment crystal growth, one‐dimensional nanocrystals are frequently employed as building blocks to synthesize two‐dimensional or large‐aspect‐ratio one‐dimensional nanocrystals. Despite recent extensive experimental advances, the underlying inter‐particle interaction in the synthesis still remains elusive. In this report, using Ag as a platform, we investigate the van der Waals interactions associated with the side‐by‐side and end‐to‐end assemblies of one‐dimensional nanorods. The size, aspect ratio, and inter‐particle separation of the Ag precursor nanorods are found to have dramatically different impacts on the van der Waals interactions in the two types of assemblies. Our work facilitates the fundamental understanding of the oriented‐attachment assembling mechanism based on one‐dimensional nanocrystals.     

二苯硫脲-醋酸丁酯萃取-石墨炉原子吸收法测定地球化学样品中痕量银

对石墨炉原子吸收光谱法测定地球化学样品中痕量银进行了研究。样品经盐酸、硝酸、硫酸、高氯酸溶解,在盐酸(1.2mol/L)介质中用醋酸丁酯萃取银与二苯硫脲螯合物,用石墨炉原子吸收光谱法测定地球化学样品中痕量银,方法检出限为0.011ng/mL,相对标准偏差(RSD,n=11)为6.0%~12.2%,加标回收率为96.00%~105.00%。能满足地球化学样品中银含量为0.02~5μg/g范围内银测定的准确度和精密度的要求。     

Preparation of fullerenol, fullerenone, and aminofullerene derivatives through selective cleavage of fullerene C-H, C-C, C-N, and C-O bonds in fullerene-mixed peroxide derivatives

Various reactions of fullerene-mixed peroxides were investigated in an effort to explore the chemistry of functional groups on the fullerene surface. Amines convert fullerene peroxides into fullerene epoxides through S_N2′ type reaction. Lewis acid catalyzed hydrolysis of fullerene epoxides led to vicinal fullerendiols, which may be oxidized into fullerendiones by diacetoxyiodobenzene (DIB). Alcohols and amines react with the adjacent dione to form acetal or hemiacetal groups through different mechanisms.     

Androgynous porphyrins. Silver(II) quinoxalinoporphyrins act as both good electron donors and acceptors

The metal-centered and macrocycle-centered electron-transfer oxidations and reductions of silver(II) porphyrins were characterized in nonaqueous media by electrochemistry, UV-vis spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The investigated compounds are {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrinato}silver(II), {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b']porphyrinato}silver(II), {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)bisquinoxalino[2,3-b':7,8-b']porphyrinato}silver(II), and {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)bisquinoxalino[2,3-b':12,13-b']porphyrinato}silver(II). The first one-electron oxidation and first one-electron reduction both occur at the metal center to produce stable compounds with Ag(III) or Ag(I) metal oxidation states, irrespective of the type of porphyrin ligand. The electrochemical HOMO-LUMO gap, determined by the difference in the first oxidation and first reduction potentials, decreases by introduction of quinoxaline groups fused to the Ag(II) porphyrin macrocycle. This provides a unique androgynous character to Ag(II) quinoxalinoporphyrins that enables them to act as both good electron donors and good electron acceptors, something not previously observed in other metalloporphyrin complexes. The second one-electron oxidation and second one-electron reduction of the compounds both occur at the porphyrin macrocycle to produce Ag(III) porphyrin pi-radical cations and Ag(I) porphyrin pi-radical anions, respectively. The macrocycle-centered oxidation potentials of each quinoxalinoporphyrin are shifted in a negative direction, while the macrocycle-centered reduction potentials are shifted in a positive direction as compared to the same electrode reactions of the porphyrin without the fused quinoxaline ring(s). Both potential shifts are due to a stabilization of the radical cations and radical anions by pi-extension of the porphyrin macrocycle after fusion of one or two quinoxaline moieties at the beta-pyrrolic positions of the macrocycle. Introduction of quinoxaline groups fused to the Ag(II) porphyrin macrocycle provides a unique androgynous character to Ag(II) quinoxalinoporphyrins that enables them to act as both good electron donors and good electron acceptors.     

Optical sectioning for microfluidics: secondary flow and mixing in a meandering microchannel

Secondary flow plays a critical function in a microchannel, such as a micromixer, because it can enhance heat and mass transfer. However, there is no experimental method to visualize the secondary flow and the associated mixing pattern in a microchannel because of difficulties in high-resolution, non-invasive, cross-sectional imaging. Here, we simultaneously imaged and quantified the secondary flow and pattern of two-liquid mixing inside a meandering square microchannel with spectral-domain Doppler optical coherence tomography. We observed an increase in the efficiency of two-liquid mixing when air was injected to produce a bubble-train flow and identified the three-dimensional enhancement mechanism behind the complex mixing phenomena. An alternating pair of counter-rotating and toroidal vortices cooperated to enhance two-liquid mixing.     

Olefin-Linked Covalent Organic Frameworks with Electronegative Channels as Cationic Highways for Sustainable Lithium Metal Battery Anodes

Despite the enormous interest in Li metal as an ideal anode material, the uncontrollable Li dendrite growth and unstable solid electrolyte interphase have plagued its practical application. These limitations can be attributed to the sluggish and uneven Li⁺ migration towards Li metal surface. Here, we report olefin-linked covalent organic frameworks (COFs) with electronegative channels for facilitating selective Li⁺ transport. The triazine rings and fluorinated groups of the COFs are introduced as electron-rich sites capable of enhancing salt dissociation and guiding uniform Li⁺ flux within the channels, resulting in a high Li⁺ transference number (0.85) and high ionic conductivity (1.78 mS cm⁻¹). The COFs are mixed with a polymeric binder to form mixed matrix membranes. These membranes enable reliable Li plating/stripping cyclability over 700 h in Li/Li symmetric cells and stable capacity retention in Li/LiFePO₄ cells, demonstrating its potential as a viable cationic highway for accelerating Li⁺ conduction.     

Beta-nitro derivatives of germanium(IV) corrolates

The reaction between germanium(IV) meso-triphenylcorrolates and nitrate salts affords the corresponding beta-nitro substituted corroles in good yield. Chromatographic separation of the crude reaction mixtures enables isolation of a mu-oxo dimer along with the corresponding monomers bearing a hydroxy or methoxy group at an axial position of the germanium central metal ion. Depending on the reaction conditions, mono- or dinitro substituted complexes can be obtained. The substitution is highly regioselective in each case, giving only the 3-nitro or 3,17-dinitro derivative among the different possible isomers. Five of the synthesized complexes were examined by cyclic voltammetry and UV-visible spectroelectrochemistry in dichloromethane, and the dinitro mu-oxo dimer is structurally characterized.